Hi Steve
Pressure relief valves are notorious for not shutting off once they have been opened - its a big mistake to depressurize things this way. The valve will need to be replaced - simple enough if the access is good. Regarding the expansion vessel, only try to pressurize it with air when the system is empty, at no pressure. Use a bike pump to take it up to 10 psi. If you depress the air schraeder valve and water squirts out, then the expansion vessel is kaput. Hope this helps!
John, September 2009